Published March, 1963
CHELATES IN SOILS-A SYMPOSIUM
Some Principles of Chelation Chemistry1
D. S. LEHMAN2
ABSTRACT
There are various factors which contribute to the
stability of a metal chelate. The number of rings formed
"by one molecule of chelating agent with the metal ion,
the size of the rings, and the nature of the donor atoms
are of prime importance. Also to be considered are the
effects of resonance stabilization and steric relationships.
Thermodynamic data shows that a favorable increase in
entropy often makes a significant contribution to the
stability of a chelate. In addition the environment, for
example, the pH, plays an important role in chelation
reactions.
"Contribution from Technical Service and Development
Dept., The Dow Chemical Co., Midland, Mich. Presented
before Div. Ill, Soil Science Society of America, Nov. 28,
1961, at St. Louis, Mo. Received Apr. 24, 1962. Approved
July 16, 1962.
2
Chemist, Technical Service and Development Dept., The
Dow Chemical Co., Midland, Mich.
I T is APPROPRIATE at the outset of this symposium on
chelates and soils that we should consider some of the
basic chemistry involved in chelation. Most of the infor-
mation to be presented in this paper is available in the
literature. Excellent reviews have been published by
Martell (7, 11, 12) and others (1, 3, 10). However, it
was felt that for the purposes of this symposium we should
attempt to summarize some of the important principles of
chelation chemistry which have become understood in
recent years. It is hoped that this will promote a fuller
appreciation of the papers to follow this one.
Chelation chemistry has become of great interest be-
cause it offers the possibility of forming complexes having
much greater stability than corresponding complexes
which cannot form the chelate structure. Chelation may
be defined as the equilibrium reaction between a metal
ion and a complexing agent, characterized by the forma-
tion of more than one bond between the metal and a
molecule of the complexing agent and resulting in the
formation of a ring structure incorporating the metal ion.
It is merely a part of the large field of coordination chem-
istry arbitrarily set apart by the above definition.
168 SOIL SCIENCE SOCIETY PROCEEDINGS 1963
LOG K , = 4.13 LOG K, = 10.72
LOG K 2 = 3.48
LOG K 3 = 2.87
LOG K4=2.ll
LOG K, K.r 7.61
LOG K, K 2 K 3 = 10.48
LOG K = 15.9
Figure 1—Stability constants for several nitrogen-con-
taining compounds with copper (II).
The term "sequestration" often appears in discussions
of metal ion complex formation. This term has been used
in a wide variety of ways and does not readily lend itself
to precise definition. It is the description of a function and
does not denote a specific chemical reaction. Sequestra-
tion is generally taken to be the reaction whereby a metal
ion is strongly complexed in such a manner that, although
remaining in solution, many of the properties of the metal
ion are modified. It is not necessary that the complex con-
tain a heterocyclic ring structure involving the metal ion
as in chelation. Sequestration is also differentiated from
chelation in that a chelate need not necessarily be soluble.
Since the term "chelation" has a more specific chemical
meaning, it will be the term of choice where applicable
in this discussion.
The first portion of this discussion will be devoted to a
consideration of factors which contribute to chelate sta-
bility. The measure of chelate stability is expressed by
stability constants, which in their simple form are as fol-
lows:
M + A <-> MA
K! = ( M A ) / ( M ) (A)
MAn + A & MA11+1
K n+1 = (MA n+1 )/(MAJ (A)
where M is the metal ion, A is the ligand, and MA is the
chelate. Thus it is seen that a high value for K means that
the ratio of chelated metal to unchelated metal is high.
In our discussion of factors contributing to chelate sta-
bility, we shall first consider the effect of the metal ion
briefly, then examine the effect of the chelating group in
greater detail.
EFFECT OF METAL ION
In many chelation reactions, the bonds formed are
ionic in character. In those cases the stability of the
chelate, for metal ions of the same family and having the
same charge, generally increases as the size of the metal
ion decreases. For example, calcium generally forms a
more stable chelate than strontium. The stability also
generally increases with increasing charge of the metal
ion. This is one reason why Fe (III) forms more stable
chelates than Fe (II) in most instances.
The metal-to-ligand bond is sometimes quite covalent in
nature. In those cases an increase in stability tends to
Table 1—Comparison of stability constants for 2 moles of
methyliminodiacetate with that for 1 mole of
ethylenediaminetetraacetate.
Methyliminodiacetate Ethylenediaminetetraacetate
logK,K 2 log K,
Cd(II) 12.52 16.59
Fe (II) 12. 02 14. 33
Mn(II) 9.56 14.04
Ni(H) 15.95 18.56
Pb(II) 12. 12 18. 04
Zn(II) 14.09 16.50
o=c
Figure 2—Comparison of methyliminodiacetate with ethy-
lenediaminetetraacetate.
follow an increase in electronegativity of the metal ion
as, for example, in going from calcium to zinc in the
periodic table. Exceptions to this are explained by the
ligand field theory and are discussed in several recent
books (2, 13).
EFFECT OF CHELATING AGENT
Number of Rings
The stability of a chelate increases with the number
of rings formed by a molecule of chelant and the metal
ion. This is illustrated by figure 1, which presents stability
constants for some nitrogen complexes of copper (7). It
is of interest to compare log KiK 2 of two moles of
ammonia with log Kj for ethylenediamine. It is seen
that hooking the two nitrogen atoms together by the
ethylene group, and thereby forming a ring structure,
results in a stability much greater than that for the two
moles of ammonia. This process can be carried one step
further with diethylenetriamine which has a log K^ of 15.9
as compared to log IQICjKg of 10.48 for three moles of
ammonia. This increase of stability with additional ring
formation is sometimes referred to as the chelate effect.
A more rigorous demonstration of the chelate effect is
shown in table 1 and figure 2. The stability constant of
two moles of methyliminodiacetic acid is compared with
the stability constant for one mole of ethylenediaminete-
traacetic acid (EDTA) ( 4 ) . One would expect very little
difference in the basicity of the nitrogen in these two
compounds. Yet it is seen that stability constant for
EDTA is more than 100 times that of two moles of methy-
liminodiacetic acid in each instance.
Size of Chelate Ring
Table 2 and figure 3 give formation constants of alka-
line earth chelates of homologs of ethylenediaminetetra-
acetic acid (14). Examination of the constants for cal-
cium, for example, shows that the five-membered ring is
the most stable, and it is generally true that five-membered
 LEHMAN: PRINCIPLES OF CHELATION CHEMISTRY 169
Table 2—Stability constants of alkaline earth chelates of Table 3—Log K MA values of some N-substituted
homologs of ethylenediaminetetraacetate. iminodiacetic acids.
Carbon atoms Log K R-N(CHjCOOH),
In bridge
Mg(II) Ca(II) Sr(II) Ba(ll) B Ca Cd Co(II) Zn
x =2 8.7 10.5 8.6 7.8 HOCHjCH,— 4.63 7.52 7.90 8.33
x=3 6.0 7.1 5.2 4.2 H 2 NCHjCH 2 — 4.63 10.58 11.78 11. 9J
5.0 HSCH, CH 2 — 4.88 16.72 14.67 15.92
x=5 4.6

M
C/ (CH 2 ) X

= 17.6 = 21.3

Figure 4—Effect of resonance on chelate stability.

Figure 3—Homologs of ethylenediaminetetraacetate.
Entropy Considerations
rings are most stable for these aliphatic groupings. How-
ever, there are instances where a six-membered chelate A study of the thermodynamic functions involved in
ring is more stable. These latter are characteristic of the chelation reaction reveals that entropy plays an im-
ligands containing aromatic rings or conjugated linkages, portant role in chelate stability. The entropy contribu-
where bond angles are wider, or where an even number tion serves to explain in part some of the previously men-
of atoms are required for resonance in the chelate ring. tioned factors contributing to chelate stability.
In many chelation reactions, negative and positive ions
Donor Atom are combined and the charges neutralized. The resulting
complex has a much weaker influence on the orientation
A comparison of three different donor atoms is given of water molecules than did the original ions. This results
in table 3 ( 4 ) , which shows iminodiacetic acid substituted in a favorable entropy increase. The importance of the
with three different ligand groups. Calcium, a metal ion entropy increase is shown in table 4, which reveals that
which forms primarily ionic type bonds, displays very for some cations—alkaline earths in particular—the entropy
little difference in stability with the three different groups. change is more important than the enthalpy change (6, 8).
Zinc, however, which has a tendency to participate also
in covalent type bonds, shows a definite preference for Another aspect of this entropy change is presented by
nitrogen over oxygen and sulphur over nitrogen. The table 5 which gives the differences in thermodynamic
above is, of course, only one example of the effect of the changes between chelate and complex formation for sev-
donor group. eral metal ions (15, 16). It will be noticed that for zinc
the change in enthalpy is approximately the same with
From the three factors that we have just considered, it both ammonia and ethylenediamine. This indicates that
is apparent that chelating agents can very easily be the nitrogen-to-zinc bond is about the same in both cases.
formed in the soil. A potentially strong chelating agent The increased stability of zinc and ethylenediamine corn-
exists whenever several donor atoms are connected by
two or three carbon atoms.
Table 4—Thermodynamic data for the formation of metal
chelates of ethylenediaminetetraacetate (tem-
Resonance Stabilization perature = 25° C.).
The contribution of resonance to chelate stability is AF- AH' AS-
demonstrated by figure 4 (4). The stability constant of kcal./mole kcal. /mole cal./'C.
ethylenediamine is appreciably less than that for 2,2'- Mg(II) -12.4 - 3 +32
Ca(II) -15.0 - 3 +42
bipydridine, a compound offering possibilities for reso- Sr(II) -11.9 - 4 +26
nance stabilization. An improvement is offered by 1,10- Ba(II) -10.5 - 4 +22
Mn (II) -17.2 -5.2 +41
phenanthroline which has a stability constant even higher Co (II) -21.4 - 4.1 +58
than the bipydridine. Ni(II) , -24.0 - 7.6 +55
Cu(II) -24.4 - 8.2 +55
Zn(II) -20.9 -4.5 +55
Cd(II) -20.5 - 9.1 +38
Steric Effects Pb(II) -23.6 -13.1 +35

The 2,2'-bipydridine chelate can also be used to illus-

trate steric hindrance. For example, if groups are substi- Table 5—Comparison of thermodynamic changes of che-
tuted in the 6 and 6' positions, the stability drops due to late formation with those of simple complex formation.
mutual repulsion between ligands. If, on the other hand,
the substitution is in the 3 and 3' positions, the decreased A(AF°) A(AH') A(TAS)
stability must be due to some other cause. It is thought kcal. kcal. kcal.
Cu(En) - Cu(NHj)j -4.30
that the groups prevent the ligand from assuming a Zn(En) - Zn(NH 3 ) 2 -1.55
-2.6
+0.1
+ 1.7
+ 1.6
coplanar configuration and hence interfere with the Cd (En) - Cd(NH 3 ) z -1.20 + 0.1 + 1.3
Cd (En) - Cd(NH 2 CH 3 ) 2 -1.40 0.0
resonance stability in the chelate. + 1.4
170 SOIL SCIENCE SOCIETY PROCEEDINGS 1963

pared to zinc and ammonia is due to the entropy change tion constant of the hydroxide complex. The solubility
favoring the formation of the ethylenediamine complex. product for ferric hydroxide is about 10~36 and at a pH
This is similarly true for cadmium with ethylenediamine of 8 or 9 it becomes difficult to get good chelation of iron
and ammonia as well as with ethylenediamine and with EDTA. In such cases it is necessary to modify the
methylamine. With copper there is a difference in the structure of the chelant to get the additional stability
change in enthalpy as well as entropy. The increase in necessary to compete successfully with the hydroxide ions.
stability of a chelate with the increase in number of rings In those cases where the hydroxide is not so extremely
formed, often called the chelate effect, can perhaps be insoluble, very effective chelation is obtained at pH's
explained in part by this favorable entropy change. from 8 to 12 by use of the aminopolycarboxylic type
materials.
EFFECT OF ENVIRONMENT In our discussion of chelation chemistry we have seen
that a sizeable research effort has provided us with a
The above discussion has examined the effect of the sound basis for understanding many of the chelation
metal ion and the chelating agent on chelate stability. reactions which occur. In our laboratories we have found
Other factors also have a bearing on the chelation equilib- these principles to be very useful in further development
rium. Some of these actually affect the equilibrium con- of ideas for research and development. We have seen
stant while others do not. Increasing the temperature these principles applied in the soil sciences to an ap-
generally results in a decrease in stability constant. It preciable extent already and are hopeful that meetings
has been our experience that for aminocarboxylic acids such as those today will provide additional impetus in
the stability constant decreases by approximately two this direction.
log units between room temperature and 100 °C. Stability
constants generally increase with decrease in dielectric
constant of the solvent and decrease with an increase in
ionic strength. These changes are relatively small and,
although they are important in precise measurements, are
probably of minor importance in most practical applica-
tions.
It is of interest to consider the effect of anions and
cations, other than that of changing the ionic strength, on
a chelation reaction. By examining a table of stability
constants it is possible to predict with some certainty the
effect of a particular metal ion or ions on a given
metal chelate and the final equilibrium of the system. The
metal ion having the highest stability constant with the
chelating agent will be the first to be chelated. Consulta-
tion of a two volume set of books entitled, "Stability
Constants" (4, 5), provides an excellent start in a search
for stability constant data.
In considering the effect of other anions one must
take into account the solubility products or the stability
constants of competing complexes which might be formed.
Where strong chelates are formed, such as with the amino
polycarboxylic acids, other anions will often have very
little effect.
A discussion of environment would not be complete
without examining the effect of pH. Since chelating
agents are generally Lewis bases, they will react with
Lewis acids, including, of course, the hydrogen ion. The
hydrogen ion is able to compete successfully with the
metal ion for the chelant in cases where the equilibrium
constant is low. For EDTA, metal ions such as iron or
copper that have a high stability constant are relatively
unaffected by low pH. However, below a pH of 5, calcium
is only very weakly chelated. A brief but helpful dis-
cussion of the use of acid dissociation constants to calcu-
late the effect of pH on apparent stability constant is
given by Flaschka (9).
At higher pH's the principal competition is expressed
by the solubility product of the hydroxide or the associa-